JP2021054814A - Dental curable composition comprising transition metal adsorbent - Google Patents

Abstract

To provide a dental curable composition having excellent curability and storage stability.SOLUTION: A dental curable composition has (a) a transition metal adsorbent in which a transition metal compound of the fourth period is adsorbed onto an inorganic particle non-reactive with transition metal compounds of the fourth period, (b) a thiourea derivative, (c) an organic peroxide having a hydroperoxide group, and (d) a polymerizable monomer. The (d) polymerizable monomer has a polymerizable monomer free of (d-1) an acidic group. The non-reactive inorganic particle has a pore volume of 0.2 cc/g or less.SELECTED DRAWING: None

Description

The present invention relates to a dental curable composition having excellent storage stability.

In the field of dentistry, curable compositions containing polymerization initiators and polymerizable monomers composed of organic peroxides and their reducing agents are dental cements, dental adhesives, dental room temperature polymerization resins, and dental pretreatments. Widely used as a material, dental abutment construction material, etc.

A paste-like package-type curable composition using an oxidation-reduction reaction of an organic peroxide and its reducing agent as a polymerization initiation reaction is known. Among them, benzoyl peroxide as an organic peroxide and aromatic as a reducing agent thereof. The sachet-type curable composition using amine has high curability and has been widely used since the past. However, when stored under conditions of high environmental temperature, problems such as low storage stability and discoloration to yellow or brown have been problems. As a solution to this problem, a package-type curable composition using a hydroperoxide which is an organic peroxide and a thiourea derivative which is a reducing agent thereof has been disclosed (Prior Document 1). Although these package-type curable compositions have improved storage stability and color tone stability as compared with conventional compositions using a polymerization initiator, their curability is insufficient.
Further, as a technique for overcoming the above problems, in addition to hydroperoxide which is an organic peroxide and a thiourea derivative which is a reducing agent thereof, a transition metal compound of the fourth cycle such as a copper compound or a vanadium compound is blended as a polymerization accelerator. A sachet-type curable composition has been presented (Prior Document 2). Although the curability of these package-type curable compositions is dramatically improved, there is a problem that the storage stability is insufficient.

Japanese Unexamined Patent Publication No. 2009-292761 Japanese Unexamined Patent Publication No. 2012-051856

Although the compounding of the transition metal compound in the fourth period is effective for the polymerization reaction, there are problems that the curability is lowered and the stability after production is low.

As a result of diligent studies to solve the above problems, by adopting a transition metal adsorbent in which a transition metal compound of the 4th period is previously adsorbed on non-reactive inorganic particles, it has excellent curability and storage stability. We have found and completed a dental curable composition.
The present invention comprises (a) a transition metal adsorbent in which a fourth-cycle transition metal compound is adsorbed on non-reactive inorganic particles, (b) a thiourea derivative, and (c) a hydroperoxide group. It contains an organic peroxide having and (d) a polymerizable monomer, and (d) the polymerizable monomer contains (d-1) a polymerizable monomer having no acidic group and is non-reactive. The dental curable composition is characterized in that the pore volume of the inorganic particles of the above is 0.2 cc / g or less.

Preferably, the (d) polymerizable monomer is a dental curable composition further comprising (d-2) a polymerizable monomer having an acidic group.
A dental curable composition containing (d-2) 1 to 40 parts by weight of a polymerizable monomer having an acidic group with respect to 100 parts by weight of the total amount of (d) the polymerizable monomer is preferable.

Preferably, the first paste is (a) a transition metal adsorbent in which the transition metal compound of the fourth cycle is adsorbed on the non-reactive inorganic particles with the transition metal compound of the fourth cycle, (b) a thiourea derivative, and ( A dental curable composition containing (d) a polymerizable monomer, the second paste containing (c) an organic peroxide having a hydroperoxide group, and (d) a polymerizable monomer.
Preferably, (a) the amount of the transition metal compound adsorbed in the 4th period in the transition metal adsorbent in which the transition metal compound in the 4th period is adsorbed on the non-reactive inorganic particles with the transition metal compound in the 4th period is 0.001. A dental curable composition of ~ 0.1 g / m ^2.
Preferably, with respect to 100 parts by weight of the total amount of the polymerizable monomer, (a) a transition metal adsorbent in which the transition metal compound of the fourth cycle is adsorbed on the inorganic particles non-reactive with the transition metal compound of the fourth cycle is 0. .05 to 7.5 parts by weight, (a) The transition metal compound contained in the transition metal adsorbent in which the transition metal compound of the fourth cycle is adsorbed on the inorganic particles that are non-reactive with the transition metal compound of the fourth cycle. A dental curable composition containing 001 to 1 part by weight, (b) 0.1 to 4 parts by weight of a thiourea derivative, and (c) 0.1 to 3 parts by weight of an organic peroxide having a hydroperoxide group. is there.
Preferably, 0.5 to 350 parts by weight of the filler, 0.01 to 5 parts by weight of the photopolymerization initiator, and 0.01 to 5 parts by weight of the polymerization accelerator are further added to 100 parts by weight of the total amount of the polymerizable monomer. It is a dental curable composition containing.

According to the present invention, a dental curable composition having excellent curability and storage stability by adopting a transition metal adsorbent in which a transition metal compound of the 4th period is previously adsorbed on non-reactive inorganic particles. Can be provided.

The present invention will be described in detail below. The transition metal adsorbent of the present invention (a) in which the transition metal compound of the 4th period is adsorbed on the non-reactive inorganic particles with the transition metal compound of the 4th period will be described.

The transition metal compound of the 4th period refers to a metal compound of groups 3 to 12 of the 4th period of the periodic table, and specifically, scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), and iron. Any metal compound of (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn) can be used without limitation. Each of the above transition metal elements may have a plurality of valences, but can be added to the curable composition of the present invention as long as it has a valence that can exist stably. For example, Sc (trivalent), Ti (tetravalent), V (3, 4 or 5 valence), Cr (2, 3 or 6 valent), Mn (2 to 7 valence), Fe (2 or trivalent), Co (divalent or trivalent), Ni (divalent), Cu (1 or divalent), Zn (divalent). Specific examples of the transition metal compound include scandium iodide (trivalent) as a scandium compound, titanium chloride (tetravalent), titanium (tetravalent) tetraisopropoxide and the like as titanium compounds, and acetylacetone vanadium (tetraisopropoxide) as a vanadium compound. Trivalent), divanadium tetraoxide (tetravalent), vanadylacetylacetonate (tetravalent), vanadium stearate (tetravalent), vanadyl oxalate (tetravalent), vanazyl sulfate (tetravalent), oxobis (1-valent) Phenyl-1,3-butandionate) vanadium (tetravalent), bis (maltlate) oxovanadium (tetravalent), vanadium pentoxide (pentavalent), sodium metavanadate (pentavalent), etc. are used as manganese compounds. Manganese (divalent), manganese naphthenate (divalent), etc., and iron compounds such as iron acetate (divalent), iron chloride (divalent), iron acetate (trivalent), iron chloride (trivalent), etc. , Cobalt compounds such as cobalt acetate (divalent) and cobalt naphthenate (divalent), nickel compounds such as nickel chloride (divalent), copper compounds such as copper chloride (monovalent) and copper bromide (monovalent). ), Copper chloride (divalent), copper acetate (divalent) and the like, and zinc chloride (divalent), zinc acetate (divalent) and the like as zinc compounds.

Among these, a trivalent or tetravalent vanadium compound is preferable, a divalent copper compound is preferable, and a trivalent or tetravalent vanadium compound having a higher polymerization promoting ability is more preferable, and a tetravalent vanadium compound is most preferable. A plurality of types of these transition metal compounds in the fourth period may be used in combination, if necessary. The blending amount of the transition metal compound is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, based on 100 parts by weight of the total amount of the total polymerizable monomer. If it is less than 0.001 part by weight, the polymerization promoting effect is insufficient, and if it exceeds 1 part by weight, it may cause discoloration or gelation of the curable composition, and the storage stability may be lowered.

The transition metal compound of the fourth cycle and the non-reactive inorganic particles (hereinafter, also simply referred to as “non-reactive inorganic particles” in the present specification) are the transition metal compounds of the fourth cycle (hereinafter, hereinafter, in the present specification). Inorganic particles that not only do not react with (also referred to as “transition metal compound”) but also do not interact with the redox reaction between the organic peroxide and the thiourea derivative which is the reducing agent thereof can be preferably used. Non-reactive inorganic particles include oxides of silica, zirconia, calcium, titania, and alumina and their composite oxides (glass), metal fluorides such as trifluoroitterbium and sodium fluoride, magnesium sulfate, barium sulfate, and the like. Sulfate etc. can be used. Among these, composite oxides, metal fluorides or sulfates are preferable, and trifluoroytterbium and barium sulfate are more preferable. A plurality of types of these non-reactive inorganic particles may be used in combination, if necessary. The primary particle size of the non-reactive inorganic particles is preferably 0.01 to 50 μm, more preferably 0.01 to 20 μm from the viewpoint of dispersibility. When the primary particle size of the non-reactive inorganic particles is 0.01 μm or less, the cohesiveness becomes high and the dispersibility in the polymerizable monomer decreases, and when it is 50 μm or more, the non-reactive inorganic particles are unevenly dispersed in the composition. This may make it difficult to sufficiently promote the polymerization.

As for the shape, non-porous particles can be used without limitation, and examples thereof include spherical, crushed, and amorphous particles. In the case of porous particles, the transition metal compound adsorbed in the pores reduces the chance of reacting as a polymerization accelerator, which not only lowers the polymerization promotion efficiency, but also causes discoloration by remaining without reacting. It may happen. Therefore, the pore volume of the non-reactive inorganic particles in the present invention is 0.2 cc / g or less, preferably 0.15 cc / g or less, and most preferably 0.1 cc / g or less. The pore volume can be determined by, for example, the BJH method, and the pore volume is that of the agglomerated particles when the non-reactive inorganic particles are agglomerated particles.

As for the method for adsorbing the transition metal compound to the non-reactive inorganic particles, either the physical adsorption method or the chemical adsorption method can be used without limitation. Specifically, chemical adsorption methods such as hydrophobic adsorption, precipitation-precipitation method, impregnation method, coprecipitation method, ion exchange method, and equilibrium adsorption method, and physical adsorption methods can be used, but physical adsorption can be used from the viewpoint of production efficiency. The method is preferred. More specifically, it is dissolved or dispersed in an organic solvent having a high affinity with the transition metal compound and having a low boiling point, mixed with non-reactive inorganic particles, and then the organic solvent is removed to adsorb the transition metal compound. A method of obtaining a body, a method of dissolving a transition metal compound in a good solvent having a high affinity with a transition metal compound, and then adding a poor solvent to precipitate transition metal particles on the surface of the inorganic particles, physically inorganic using a pot mill, a ball mill, a planetary mill, or the like. A method of adsorbing the transition metal compound on the particle surface is preferable.

The amount of the transition metal compound adsorbed on the non-reactive inorganic particles ^{is preferably 0.001 to 0.1 g / m 2 in} terms of the amount of adsorption per unit area of the inorganic particles, and more preferably 0.001 to 0.05 g. / M ² . If it is 0.001 g / m ² or less, the polymerization promoting effect is insufficient, and if it is 0.1 g / m ² or more, the polymerization promoting effect is excessive and discoloration or the like may occur, resulting in a decrease in storage stability. In the present invention, when a plurality of (a) transition metal adsorbents in which the transition metal compound of the fourth cycle is adsorbed on a plurality of (a) transition metal compounds of the fourth cycle and non-reactive inorganic particles are included, either (a). ) It is preferable that the amount of adsorption in the transition metal adsorbent in which the transition metal compound of the fourth cycle is adsorbed on the transition metal compound of the fourth cycle and the non-reactive inorganic particles is in the above range, and all (a) fourth. It is more preferable that the amount of adsorption in the transition metal adsorbent in which the transition metal compound of the fourth cycle is adsorbed on the transition metal compound of the period and the non-reactive inorganic particles is in the above range.

(A) The blending amount of the transition metal adsorbent in which the transition metal compound of the 4th period is adsorbed on the transition metal compound of the 4th period and the non-reactive inorganic particles is 100 parts by weight of the total amount of the total polymerizable monomer. It is preferably 0.05 to 7.5 parts by weight, more preferably 0.05 to 5 parts by weight. If it is less than 0.05 parts by weight, the ability as a polymerization accelerator is insufficient, and if it exceeds 7.5 parts by weight, it may be localized and discolored.

The thiourea derivative (b) of the present invention can be used without limitation as long as it is a known thiourea derivative. Specific examples of the thiourea derivative include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl) thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, and N-allyl-N'-(2-). Hydroxyethyl) thiourea, N-benzyl thiourea, 1,3-dicyclohexylthiourea, N, N'-diphenylthiourea, 1,3-di (p-tolyl) thiourea, 1-methyl-3-phenylthiourea, Examples thereof include N-acetylthiourea, N-benzoylthiourea, diphenylthiourea and dicyclohexylthiourea. Among these, N-acetylthiourea and N-benzoylthiourea are preferable. A plurality of types of these thiourea derivatives may be used in combination, if necessary. The blending amount of the thiourea derivative is preferably 0.1 to 4 parts by weight with respect to the total amount of the total polymerizable monomer. If it is less than 0.1 part by weight, the polymerization promoting ability is insufficient, and if it exceeds 4 parts by weight, the storage stability may be lowered.

The organic peroxide having a hydroperoxide group (c) of the present invention can be used without limitation as long as it is a known organic peroxide having a hydroperoxide group. Specific examples of organic peroxides include t-butyl hydroperoxide, cyclohexyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethyl. Examples thereof include butyl hydroperoxide, and cumene hydroperoxide is preferable from the viewpoint of reactivity. A plurality of types of these organic peroxides may be used in combination, if necessary. The blending amount of the organic peroxide having a hydroperoxide group is preferably 0.1 to 3 parts by weight with respect to the total amount of the total polymerizable monomer. If it is less than 0.1 part by weight, the ability as a polymerization accelerator is insufficient, and if it exceeds 3 parts by weight, the storage stability may be lowered.

The (d) polymerizable monomer of the present invention contains (d-1) a polymerizable monomer having no acidic group. The (d) polymerizable monomer preferably contains (d-2) a polymerizable monomer having an acidic group. The (d) polymerizable monomer may be composed of only the (d-1) polymerizable monomer having no acidic group.
The polymerizable monomer having no acidic group (d-1) of the present invention can be used without limitation as long as it has one or more polymerizable groups and is known. A polymerizable monomer in which the polymerizable group exhibits radical polymerizable properties is preferable, and specifically, from the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth) acrylic group and / or a (meth) acrylamide group. In the present specification, "(meth) acrylic" means acrylic and / or methacrylic, "(meth) acryloyl" means acryloyl and / or methacryloyl, and "(meth) acrylate" means acrylate and / or methacrylic. / Or Means Methacrylate.

Examples of the polymerizable monomer having one radically polymerizable group and no acidic group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 6-Hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N- Hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 11- (meth) acryloyloxyundecyl Examples thereof include trimethoxysilane and (meth) acrylamide. Among these, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate or erythritol mono ( Meta) acrylate is preferred.

As the polymerizable monomer having two radically polymerizable groups and not having an acidic group, 2,2-bis ((meth) acryloyloxyphenyl) propane and 2,2-bis [4- (3- (meth)) ) Acryloyloxy) -2-hydroxypropoxyphenyl] Propane (commonly known as "Bis-GMA"), 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (meth) acryloyl) Oxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane), 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2- Bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2 -(4- (Meta) acryloyloxydiethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyditrimethylethoxyphenyl) propane, 2- (4) -(Meta) acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (Meta) acryloyloxyisopropoxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyethyl) pyromerylate, glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butane Didiol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-bis (3) − Methacryloyloxy-2-hydroxypropoxy) ethane, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as “” UDMA "), 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane and the like. Among these, from the viewpoint of mechanical strength, 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] Propane, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate and 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane are preferred, and triethylene from the viewpoint of handleability. Glycoldi (meth) acrylates, neopentyl glycol di (meth) acrylates and glycerol di (meth) acrylates are preferred. Among 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, a compound having an average addition mole number of ethoxy group of 2.6 (commonly known as “D2.6E”) is preferable.

Examples of the polymerizable monomer having three or more radically polymerizable groups and no acidic group include trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, and trimethylolmethane tri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane -1,3-diol] Tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane and the like can be mentioned. Among these, trimethylolpropane tri (meth) acrylate is preferable because the obtained curable composition has high mechanical strength.

A plurality of types of these (d-1) polymerizable monomers having no acidic group may be used in combination, if necessary. From the viewpoint of improving mechanical properties, the blending amount of the polymerizable monomer having two or more radically polymerizable groups and having no acidic group is 40 out of 100 parts by weight of the total amount of the polymerizable monomer in the curable composition. It is preferably set to -100 parts by weight, more preferably 60-90 parts by weight. Further, if the blending amount of the polymerizable monomer having two or more radically polymerizable groups and not having an acidic group is less than 40 parts by weight, the mechanical properties may be lowered.

The curable composition of the present invention may be blended with a polymerizable monomer having an acidic group (d-2) for the purpose of imparting adhesiveness to a prosthetic device to be attached to the dentin or the oral cavity. (D-2) The polymerizable monomer having an acidic group has one or more polymerizable groups and has a phosphoric acid group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, a carboxylic acid group and the like as acidic groups. Any polymerizable monomer having at least one acidic group of the above can be used without limitation.

As a polymerizable monomer having an acidic group having a phosphoric acid group, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxy. Butyldihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) Acryloyloxyoctyldihydrogenphosphate, 9- (meth) acryloyloxynonyldihydrogenphosphate, 10- (meth) acryloyloxydecyldihydrogenphosphate, 11- (meth) acryloyloxyundecyldihydrogenphosphate, 12- (Meta) acryloyl oxide decyldihydrogen phosphate, 16- (meth) acryloyloxyhexadecyldihydrogen phosphate, 20- (meth) acryloyloxyicosyldihydrogen phosphate, bis [2- (meth) acryloyloxyethyl] Hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyl oxynonyl] hydrogen phosphate, bis [10- (meth) acryloyl oxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) Acryloyloxyethylphenylhydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethylhydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate; these acids Chloride, alkali metal salt, ammonium salt; and (meth) acrylamide compound in which the ester bond of these compounds is replaced with an amide bond can be mentioned.

Examples of the polymerizable monomer having an acidic group having a pyrophosphate group include bis pyrophosphate [2- (meth) acryloyloxyethyl], bis pyrophosphate [4- (meth) acryloyloxybutyl], and bis pyrophosphate [6]. -(Meta) acryloyloxyhexyl], bis pyrophosphate [8- (meth) acryloyloxyoctyl], bis pyrophosphate [10- (meth) acryloyloxydecyl]; these acid compounds, alkali metal salts, ammonium salts; And (meth) acrylamide compounds in which the ester bonds of these compounds are replaced with amide bonds and the like.

Examples of the polymerizable monomer having an acidic group having a thiophosphate group include 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, and 4- (meth). Acryloyloxybutyl dihydrogenthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthiophosphate , 8- (Meta) acryloyloxyoctyldihydrogenthiophosphate, 9- (meth) acryloyloxynonyldihydrogenthiophosphate, 10- (meth) acryloyloxydecyldihydrogenthiophosphate, 11- (meth) acryloyloxy Undecyldihydrogenthiophosphate, 12- (meth) acryloyl oxide decyldihydrogenthiophosphate, 16- (meth) acryloyloxyhexadecyldihydrogenthiophosphate, 20- (meth) acryloyloxyicosyldihydrogenthio Phosphates; these acidified compounds, alkali metal salts, ammonium salts; and (meth) acrylamide compounds in which the ester bonds of these compounds are replaced with amide bonds can be mentioned.

As the polymerizable monomer having an acidic group having a phosphonic acid group, 2- (meth) acryloyloxyethylphenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, 6- (meth) Acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyl Examples thereof include oxydecyl-3-phosphonoacetate; these acidified products, alkali metal salts, ammonium salts; and (meth) acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

Examples of the polymerizable monomer having an acidic group having a sulfonic acid group include 2- (meth) acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl (meth) acrylate.

The polymerizable monomer having an acidic group having a carboxylic acid group includes a (meth) acrylic compound having one carboxyl group in the molecule and a (meth) acrylic compound having a plurality of carboxyl groups in the molecule. Can be mentioned. Examples of the (meth) acrylic compound having one carboxyl group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloyl aspartic acid, O- (meth) acryloyl tyrosine, and N. -(Meta) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-( Meta) acryloyloxy benzoic acid, 3- (meth) acryloyloxy benzoic acid, 4- (meth) acryloyloxy benzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid , 2- (Meta) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogenphthalate, 2- (meth) acryloyloxyethyl hydrogenmalate; these acid halides; and esters of these compounds Examples thereof include (meth) acrylamide compounds in which the bond is replaced with an amide bond. Examples of the (meth) acrylic compound having a plurality of carboxyl groups in the molecule include 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid and 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid. 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meth) acryloyloxidedecane-1,1-dicarboxylic acid, 13- (Meta) Acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimerite, 4- (meth) acryloyloxybutyl trimerite, 4- (meth) acryloyloxyhexyl trimerite 4- (Meta) acryloyloxydecyl trimerite, 2- (meth) acryloyloxyethyl-3'-(meth) acryloyloxy-2'-(3,4-dicarboxybenzoyloxy) propylsuccinate; Examples thereof include acid anhydrides, acid halides; and (meth) acrylamide compounds in which the ester bonds of these compounds are replaced with amide bonds.

Among the above-mentioned polymerizable monomers having an acidic group, it is preferable to have a phosphoric acid group or a phosphonic acid group from the viewpoint of adhesiveness of the dental polymerizable composition. Among them, it is preferable to have an alkyl group or an alkylene group having 4 or more carbon atoms in the main chain in the molecule, and 10- (meth) acryloyloxydecyldihydrogen phosphate or (6-methacryloyloxy) hexylphosphonoacetate is more preferable. preferable. A plurality of types of polymerizable monomers having these acidic groups may be used in combination, if necessary. Further, the blending amount of the polymerizable monomer having an acidic group is preferably 1 to 40 parts by weight, preferably 2 to 20 parts by weight, out of 100 parts by weight of the total amount of the total polymerizable monomer from the viewpoint of adhesiveness. More preferred.

The curable composition of the present invention is not limited as long as it is a known filler, and a filler can be blended according to its use. For example, when used as a dental adhesive such as a dental direct restoration adhesive (bonding material) or a dental indirect restoration adhesive, or as a dental restoration material as a dental prosthesis such as a composite resin, it is inorganic. It is preferable to blend a filler such as a filler, an organic filler, or an organic-inorganic composite filler. The filler is preferably silane treated. By silane treatment, a large amount can be filled in the composition. As the silane treatment agent, a usual silane treatment agent can be used.

Examples of the above-mentioned inorganic filler include quartz, silica, silica-alumina, silica-titania, silica-zirconia, silica-magnesia, silica-calcia, silica-valium oxide, silica-strontium oxide, and silica-titania-sodium oxide. Examples thereof include silica-titania-potassium oxide, titania, zirconia, alumina, and glass filler. More specific glass fillers include silicate glass, fluoroaluminosilicate glass, fluoroboroaluminosilicate glass, barium glass and the like. If necessary, these inorganic fillers may be surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, ε-methacryloxyoctyltrimethoxysilane, or vinyltrimethoxysilane.

Examples of the organic filler include polymethylmethacrylate, polyethylmethacrylate, methylmethacrylate-ethylmethacrylate copolymer, ethylmethacrylate-butylmethacrylate copolymer, methylmethacrylate-trimethylolpropanemethacrylate copolymer, polyvinylchloride, polystyrene, and the like. Examples thereof include polymers such as chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

Examples of the organic-inorganic composite filler include pulverized composites of the above-mentioned inorganic oxide (inorganic filler) and polymer (organic filler).

The particle shape of the various fillers described above is not particularly limited, and pulverized particles or spherical particles as obtained by ordinary pulverization may be used. The particle size of these fillers is also not particularly limited, but is generally preferably 100 μm or less, particularly preferably 30 μm or less, from the viewpoint of dispersibility and the like. The blending amount of the filler is preferably 0.5 to 350 parts by weight, more preferably 1 to 300 parts by weight, based on 100 parts by weight of the total amount of the polymerizable monomer.

A photopolymerization initiator may be added to the curable composition of the present invention for the purpose of imparting photopolymerizability. Examples of the photopolymerization initiator include α-diketones, mono-, bis- or trisacylphosphine oxide compounds, mono- and di-acyl germanium compounds. The blending amount of the photopolymerization initiator is not particularly limited, but from the viewpoint of photocurability, 0.01 to 5 parts by weight is preferable with respect to 100 parts by weight of the total amount of the polymerizable monomer, and 0.1 to 3 parts by weight is preferable. The portion is more preferable.

Examples of α-diketones include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrene quinone, 4,4'-oxybenzyl, acenaphthenquinone and the like. .. Among these, camphorquinone is preferable because it has excellent photocurability in the visible and near-ultraviolet regions and exhibits sufficient photocurability regardless of whether a halogen lamp, a light emitting diode (LED), or a xenon lamp is used.

Examples of the mono-, bis- or trisacylphosphine oxide compounds include bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, and bis. (2,6-dimethoxybenzoyl) -n-butylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2-methylpropi-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1- Methylpropi-1-yl) phosphine oxide, bis (2,6-dimethoxybenzoyl) -t-butylphosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2,6-dimethoxybenzoyl) octylphosphine oxide , Bis (2-methoxybenzoyl) (2-methylpropi-1-yl) phosphine oxide, bis (2-methoxybenzoyl) (1-methylpropi-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) ( 2-Methylpropi-1-yl) phosphine oxide, bis (2,6-diethoxybenzoyl) (1-methylpropi-1-yl) phosphine oxide, bis (2,6-dibutoxybenzoyl) (2-methylpropi-1-yl) Il) phosphine oxide, bis (2,4-dimethoxybenzoyl) (2-methylpropi-1-yl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, bis (2,4,6-trimethylbenzoyl) (2,4-dipentoxyphenyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) benzyl phosphine oxide, bis (2,6-dimethoxybenzoyl)- 2-Phenylpropylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, bis (2,6-dimethoxybenzoyl) benzylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylpropi Luphosphine oxide, bis (2,6-dimethoxybenzoyl) -2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis (2,4,6) -Trimethylbenzoyl) isobu Examples thereof include tylphosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide. Of these, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide is preferable from the viewpoint of photocurability.

Examples of the mono- and di-acyl germanium compounds are bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis (4-methoxybenzoyl) dimethylgermanium, and bis (4-methoxybenzoyl) diethylgermanium. Examples thereof include (4-methoxybenzoyl) diethyl germanium.

The curable composition of the present invention may further contain a polymerization accelerator in order to further improve the curability. Examples of the polymerization accelerator include aliphatic amines, aromatic amines, sulfinic acid derivatives, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, borate compounds, barbituric acid derivatives, triazine compounds, halogen compounds, etc. Can be mentioned. The blending amount of the polymerization accelerator is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total amount of the polymerizable monomer.

Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine and dibutylamine; N-methyldiethanolamine and N-. Ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl (meth) acrylate, N-methyldiethanolamine di (meth) acrylate, N-ethyldiethanolamine di (meth) acrylate, triethanolamine Examples thereof include tertiary aliphatic amines such as mono (meth) acrylate, triethanolamine di (meth) acrylate, triethanolamine tri (meth) acrylate, triethanolamine, trimethylamine, triethylamine and tributylamine. Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the composition, and among them, 2- (dimethylamino) ethyl (meth) acrylate and N-methyldiethanolamine di (meth) acrylate are preferable. preferable.

Examples of the aromatic amine compound include 2,2- [3- (methylphenyl) imino] bisethanol acetate, 1,1-[(4-methylphenyl) imino] bis (2-propanol), p-toludiethanolamine, and the like. N, N-bis (2,2,2-trifluoroethyl) -p-toluidine, N, N-di (1-hydroxyethyl) -p-toluidine, N, N-di (2-hydroxypropyl) -p -Toluidine, N- (1-cyanoethyl) -N- (1-acetoxyethyl) -m-toluidine, N, N-di (1-chloroethyl) -p-toluidine, N, N-dimethyl-p-toluidine, N -Ethyl-N-methylaniline, N, N-dimethyl-aniline, N, N-dipropyl-o-toluidine, N, N-dipropyl-m-toluidine, N, N-dipropyl-p-toluidine, 4-dimethylamino Examples thereof include ethyl benzoate. Among these aromatic amine compounds, ethyl 4-dimethylaminobenzoate is preferably used from the viewpoint of excellent solubility in a polymerizable monomer and storage stability.

Examples of the sulfinic acid derivative include p-toluenesulfinic acid, benzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-triethylbenzenesulfinic acid, 2,4,6-triisopropylbenzenesulfinic acid and the like. (Preferably alkali metals or alkaline earth metals), and specific examples of these sulfinic acid salt compounds include sodium p-toluenesulfinate and sodium benzenesulfinate.

Examples of the sulfur-containing reducing inorganic compound include sulfite, bicarbonate, pyrosulfite, thiosulfate, thionate, bisulfite and the like, and specific examples thereof include sodium sulfite and potassium sulfite. , Calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite and the like.

Examples of the nitrogen-containing reducing inorganic compound include nitrite, and specific examples thereof include sodium nitrite, potassium nitrite, calcium nitrite, ammonium nitrite and the like.

Examples of the borate compound include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, and trialkyl [3,5-]. Bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (P-Butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron And trialkyl (m-octyloxyphenyl) boron (alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) and salts thereof (sodium salt). , Lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylki Norinium salt, etc.).

Examples of barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, and 5-ethylbarbituric acid. Acids, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbiturate Tool acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid , 1,3-Dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5- Methyl barbituric acid, 1-cyclohexyl-5-ethyl barbituric acid, 1-cyclohexyl-5-octyl barbituric acid, 1-cyclohexyl-5-hexyl barbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1 Examples thereof include salts of −benzyl-5-phenylbarbituric acid and thiobarbituric acids (preferably alkali metals or alkaline earth metals), and specific examples of the salts of these barbituric acids include 5-butylbarbiturates. Examples thereof include sodium toolate, sodium 1,3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethylbarbiturate.

Examples of triazine compounds include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, and 2-methyl-4,6-bis (trichloromethyl). ) -S-Triazine, 2-Methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) ) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- [2- (P-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (o-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine , 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-bis (2- {2- {N, N-bis (2- Hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ethoxy] -4,6-bis (trichloromethyl) -s-to Examples thereof include liazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine.

Examples of the halogen compound include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like.

The curable composition of the present invention may contain a metal supplement to further improve storage stability. The curability of the curable composition of the present invention is significantly changed by contamination with a trace amount of metal elements. Supplementing metals such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents in order to minimize the influence of the contamination of metal elements in the raw materials and the contamination of metal elements in the raw materials on the curability. The material may be blended. Aminocarboxylic acid-based chelating agents include ethylenediaminetetraacetic acid or its sodium salt, nitrilotriacetic acid or its sodium salt, diethylenetriaminepentacetic acid or its sodium salt, N- (2-hydroxyethyl) ethylenediaminetriacetic acid or its sodium salt, and triethylene. Tetramine N, N, N', N'', N''', N'''-hexacetic acid or its sodium salt, 1,3-propanediamine-N, N, N', N'-tetraacetic acid or its Sodium salt, 1,3-diamino-2-propanol-N, N, N', N'-tetraacetic acid or its sodium salt, hydroxyethyliminodiacetic acid or its sodium salt, N, N-di (2-hydroxyethyl) ) Glycin or its sodium salt, glycol ether diaminetetraacetic acid or its sodium salt. Examples of the phosphonic acid-based chelating agent include etidronic acid or a sodium salt thereof, nitrilotris (methylenephosphonic acid) or a sodium salt thereof, 2-phosphonobutane-1,2,4-tricarboxylic acid or a sodium salt thereof. Of these, ethylenediaminetetraacetic acid or a sodium salt thereof is preferable from the viewpoint of metal capture ability. A plurality of types of these metal supplements may be used in combination, if necessary. Further, the blending amount of the metal supplement is preferably 1 part by weight or less with respect to the total amount of the total polymerizable monomer from the viewpoint of curability, and if it exceeds 1 part by weight, the curability of the composition may decrease.

Further, a known additive can be added to the polymerizable composition of the present invention as long as the performance is not deteriorated. Examples of such additives include polymerization inhibitors, antioxidants, pigments, dyes, ultraviolet absorbers, organic solvents, thickeners and the like.

The dental curable composition of the present invention can be a two-paste type composed of a first paste and a second paste. In this case, the mixing ratio of the first paste and the second paste is usually 1: 7 to 7: 1, preferably 1: 4 to 4: 1, and more preferably 1: 2 to 2: 1 in terms of volume ratio. , Most preferably 1: 1. The mixing ratio of the first paste and the second paste can be set within a range that satisfies the desired ratio for each component.

The dental curable composition of the present invention in the case of the two-paste type can be produced by a step of uniformly mixing each material with a kneading device such as a double planetary mixer or a rotation / revolution mixer.

In the dental curable composition of the present invention, (a) a transition metal compound of the 4th period, (b) a thiourea derivative, and (c) an organic peroxide having a hydroperoxide group are indispensable for the polymerization initiation reaction. There is no such thing. The compounding combination with the first and second pastes can be appropriately selected, but the first paste is (a) a transition metal compound of the fourth period and a transition metal of the fourth period to non-reactive inorganic particles. A transition metal adsorbent adsorbing a compound, (b) a thiourea derivative, and (d) an organic peroxide containing a polymerizable monomer and the second paste having (c) a hydroperoxide group, and (d). ) It is preferable to contain a polymerizable monomer.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The abbreviations used below are as follows.

[Manufacturing of transition metal adsorbent]
The method for producing a transition metal adsorbent in which the transition metal compound of the 4th period is adsorbed on the non-reactive inorganic particles of the transition metal compound of the 4th period is as follows.
(Transition metal adsorbent 1)
Barium sulfate (BMH-40: manufactured by Sakai Chemical Industry Co., Ltd.) with an average particle size of 4.5 μm, a pore volume of 0.06 cc / g, and a specific surface area of 5.2 m ^{2 / g in a eggplant flask, vanadyl acetylacetonate (hereinafter,} (VOA: Tokyo Chemical Industry Co., Ltd.) was added in 1 g and added to 20 g of absolute ethanol, and dispersed in an ultrasonic cleaner for 10 minutes. Then, ethanol was removed under reduced pressure using an evaporator and then vacuum dried for 24 hours to obtain a transition metal adsorbent 1 in which a transition metal compound of ^{0.0192 g / m 2 was adsorbed on the surface.}
(Transition metal adsorbent 2)
After putting 10 g of trifluoroitterbium (manufactured by Tribach) with an average particle size of 0.2 μm, a pore volume of 0.05 cc / g, and a specific surface area of 8.1 m ² / g, and 1 g of VOA into the pot, put an alumina ball of φ2 mm. Add 200 g and treat with a planetary mill (Fritsch: P-5 planetary ball mill Classic Line) at 200 rpm for 2 minutes, then pass through # 200 mesh to adsorb 0.0124 g / m ² of transition metal compound to the surface. The transition metal adsorbent 2 was obtained.
(Transition metal adsorbent 3)
Barium sulfate (BMH-10: manufactured by Sakai Chemical Industry Co., Ltd.) with an average particle size of 12.0 μm, a pore volume of 0.04 cc / g, and a specific surface area of 2.2 m ^{2 / g in a eggplant flask, vanadium stearate (hereinafter,} VOS: Tokyo Kasei Kogyo Co., Ltd.) was added in 1 g and added to 20 g of absolute ethanol, and dispersed in an ultrasonic cleaner for 10 minutes. Then, ethanol was removed under reduced pressure using an evaporator and then vacuum dried for 24 hours ^{to obtain a transition metal adsorbent 3 in which 0.0454 g / m 2} of the transition metal compound was adsorbed on the surface.
(Transition metal adsorbent 4)
In a eggplant flask, 10 g of barium sulfate (BF-40: manufactured by Sakai Chemical Industry Co., Ltd.) and 1 g of VOA having an average particle size of 0.015 μm, a pore volume of 0.09 cc / g, and a specific surface area of 90 m ^{2 / g were put into 20 g of absolute ethanol.} In addition, it was dispersed in an ultrasonic cleaner for 10 minutes. Then, ethanol was removed under reduced pressure using an evaporator and then vacuum dried for 24 hours ^{to obtain a transition metal adsorbent 4 in which 0.00111 g / m 2} of the transition metal compound was adsorbed on the surface.
(Transition metal adsorbent 5)
Barium sulfate (BMH-40: manufactured by Sakai Chemical Industry Co., Ltd.) with an average particle size of 4.5 μm, a pore volume of 0.06 cc / g, and a specific surface area of 5.2 m ^{2 / g, and 2 g of VOA are placed in a eggplant flask and added to anhydrous ethanol.} It was added to 20 g and dispersed in an ultrasonic cleaner for 10 minutes. Then, ethanol was removed under reduced pressure using an evaporator and then vacuum dried for 24 hours ^{to obtain a transition metal adsorbent 5 in which 0.03846 g / m 2} of the transition metal compound was adsorbed on the surface.
(Transition metal adsorbent 6)
50 g of barium sulfate (BMH-40: manufactured by Sakai Chemical Industry Co., Ltd.) with an average particle size of 4.5 μm, a pore volume of 0.06 cc / g, and a specific surface area of 5.2 m ^{2 / g and 1 g of VOA are put into a eggplant flask and anhydrous ethanol is added.} It was added to 20 g and dispersed in an ultrasonic cleaner for 10 minutes. Then, ethanol was removed under reduced pressure using an evaporator and then vacuum dried for 24 hours ^{to obtain a transition metal adsorbent 6 in which 0.00385 g / m 2} of the transition metal compound was adsorbed on the surface.
(Transition metal adsorbent 7)
After putting 10 g of spherical silica particles (SO-C6: manufactured by Admafine Co., Ltd.) having an average particle diameter of 1.4 μm, a pore volume of 0.01 cc / g, and a specific surface area of 4.2 m ^{2 / g into the pot, and 1 g of VOA, φ2 mm} Add 200 g of alumina ball stones and treat with a planetary mill (Fritsch: P-5 planetary ball mill classic line) at 200 rpm for 2 minutes, and then pass through # 200 mesh to pass 0.0238 g / m ² of transition metal compound. A transition metal adsorbent 7 adsorbed on the surface was obtained.
(Transition metal adsorbent 8)
After putting 10 g of spherical silica particles (SO-C1: manufactured by Admafine) with an average particle diameter of 0.3 μm, a pore volume of 0.01 cc / g, and a specific surface area of 14.6 m ^{2 / g into the pot, and 2 g of VOA, φ2 mm} Add 200 g of alumina ball stones and treat with a planetary mill (Fritsch: P-5 planetary ball mill Classic Line) at 200 rpm for 2 minutes, and then pass through # 200 mesh to obtain 0.0137 g / m ² of transition metal compound. A transition metal adsorbent 8 adsorbed on the surface was obtained.
(Transition metal adsorbent 9)
Aluminosilicate glass particles (SiO ₂ 32.2%, Al ₂ O ₃ 19.3%, SrO 26) having an average particle diameter of 0.5 μm, a pore volume of 0.11 cc / g, and a specific surface area of 12.3 m ^{2 / g in the pot.} 9.9%, F8.7%, Na ₂ O 4.0%, B _{2 O 3} 8.9%: Matsukaze Seisakusho, crushed product) 10g, 1g of VOA, then 200g of φ2mm alumina ball stone is added to the planetary mill (Fritsch) ^{A transition metal adsorbent 9 in which 0.0081 g / m 2} of a transition metal compound is adsorbed on the surface through a # 200 mesh after being treated at 200 rpm for 2 minutes with a P-5 planetary ball mill Classic Line). Got
(Transition metal adsorbent 10)
Porous silica zirconia particles (SiO ₂ 92.1%, ZrO 7.8%, others 0.1%) having an average particle diameter of 3 μm, a pore volume of 0.21 cc / g, and a specific surface area of 120 m ^{2 / g in the pot: Matsukaze Manufacturing} ) After adding 10 g and 5 g of VOA, add 200 g of φ2 mm alumina ball stone, process with a planetary mill (Fritsch: P-5 planetary ball mill classic line) at 200 rpm for 2 minutes, pass through # 200 mesh, and 0. A transition metal adsorbent 10 was obtained by adsorbing a transition metal compound of .00417 g / m ^{2 on the surface.}
(Transition metal adsorbent 11)
In a eggplant flask, 10 g of barium sulfate (BMH-10: manufactured by Sakai Chemical Industry Co., Ltd.) and 2 g of VOS having an average particle size of 12.0 μm, a pore volume of 0.04 cc / g, and a specific surface area of 2.2 m ^{2 / g are put into anhydrous ethanol.} It was added to 20 g and dispersed in an ultrasonic cleaner for 10 minutes. Then, ethanol was removed under reduced pressure using an evaporator and then vacuum dried for 24 hours ^{to obtain a transition metal adsorbent 11 in which 0.09091 g / m 2} of the transition metal compound was adsorbed on the surface.
(Transition metal adsorbent 12)
20 g of barium sulfate (BF-40: manufactured by Sakai Chemical Industry Co., Ltd.) and 1 g of VOA having an average particle size of 0.015 μm, a pore volume of 0.09 cc / g, and a specific surface area of 90 m ^{2 / g were put into a eggplant flask in 20 g of absolute ethanol.} In addition, it was dispersed in an ultrasonic cleaner for 10 minutes. Then, ethanol was removed under reduced pressure using an evaporator and then vacuum dried for 24 hours ^{to obtain a transition metal adsorbent 12 in which 0.00056 g / m 2} of the transition metal compound was adsorbed on the surface.
(Transition metal adsorbent 13)
In the eggplant flask, 10 g of PMMA particles (MB-8C: Sekisui Plastics Co., Ltd.) with an average particle size of 8.3 μm and a specific surface area of 4.3 m ² / g and 1 g of VOS were added to 50 g of absolute ethanol, and inside the ultrasonic cleaner. Was dispersed for 10 minutes. Then, ethanol was removed under reduced pressure using an evaporator and then vacuum dried for 24 hours to obtain a transition metal adsorbent 13 in which a transition metal compound of ^{0.0233 g / m 2 was adsorbed on the surface.}
(Transition metal adsorbent A)
After putting 10 g of porous crosslinked PMMA particles (MBP-8: Sekisui Plastics Co., Ltd.) with an average particle size of 8.1 μm and a specific surface area of 86 m ^{2 / g and 2 g of VOA into the pot, 200 g of φ2 mm alumina balls are added to the planet mill (MBP-8: Sekisui Plastics Co., Ltd.).} The treatment was carried out at 200 rpm for 2 minutes with a P-5 planetary ball mill Classic Line manufactured by Frichchu. Although it was taken out of the pot, it was confirmed that it could not be used as an adsorbent because it was strongly aggregated and agglomerated.

[(B) Thiourea derivative]
ATU: N-acetylthiourea BTU: N-benzoylthiourea

[(C) Organic peroxide having a hydroperoxide group]
CHP: Cumene hydroperoxide t-BHP: t-Butyl hydroperoxide

[(D-1) Polymerizable monomer having no acidic group]
Bis-GMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] Propane UDMA: 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate 2.6E : 2,2-Bis (4-methacryloyloxypolyethoxyphenyl) propane TEGDMA: triethylene glycol dimethacrylate NPG: neopentyl glycol dimethacrylate 2-HEMA: 2-hydroxy, which has an average addition molar number of 2.6 ethoxy groups. Ethyl methacrylate GDMA: glycerol dimethacrylate

[(D-2) Polymerizable monomer having an acidic group]
MDP: 10-methacryloyloxydecyldihydrogen phosphate 6-MHPA: (6-methacryloyloxy) hexylphosphonoacetate 4-MET: 4-methacryloyloxyethyl trimerite

[Filler 1]
10.0 g of water, 80.0 g of ethanol, 0.020 g of phosphoric acid, 3-methacryloyloxypropyltri as a silane coupling material, with respect to 100.0 g of Schott's glass filler (GM344923: average particle size: 0.8 μm). 10.0 g of methoxysilane was stirred at room temperature for 2 hours, the obtained silane coupling treatment solution was added, and the mixture was stirred and mixed for 30 minutes. Then, the heat treatment was performed at 140 ° C. for 15 hours to obtain a filler 1.
[Filler 2]
10.0 g of water, 80.0 g of ethanol, 0.020 g of phosphoric acid, 3-as a silane coupling material, with respect to 100.0 g of spherical silica filler (SO-C2: average particle size: 0.5 μm) manufactured by Admatex. 5.0 g of methacryloyloxypropyltrimethoxysilane was stirred at room temperature for 2 hours, the obtained silane coupling treatment solution was added, and the mixture was stirred and mixed for 30 minutes. Then, the heat treatment was performed at 140 ° C. for 15 hours to obtain a filler 2.

[Other]
CQ: Camphorquinone (photopolymerization initiator)
APO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (photopolymerization initiator)
BHT: 2,6-di-t-butyl-4-methylphenol (polymerization inhibitor)
EDTA: Sodium ethylenediaminetetraacetate (metal supplement)
DMBE: Ethyl 4-dimethylaminobenzoate (polymerization accelerator)
VOA: Vanadyl acetylacetonate (same material used for transition metal adsorbents)

[Paste manufacturing method]
For each of the first or second pastes shown in Tables 1-3, (b) thiourea derivatives, (c) organic peroxides with hydroperoxide groups, and (d) polymerizable without acidic groups. A monomer, (e) a polymerizable monomer having an acidic group, and the like were added to a mixing vessel and mixed using a mix rotor VMRC-5 at 100 rpm for 24 hours to obtain a resin solution. Then, the filler, (a) a transition metal adsorbent in which the transition metal compound of the 4th period is adsorbed on non-reactive inorganic particles is put into a kneading container, and kneaded at 1400 rpm for 20 minutes using a rotation / revolution mixer ARV-300. Then, the first paste and the second paste were obtained. The obtained first paste and second paste are filled in a 5 mL double syringe manufactured by Mixpack (volume ratio of first paste to second paste is 1: 1) so as to have a predetermined weight component ratio. The prepared compositions 1 to 31 were prepared as a dental two-paste type polymerizable composition.

[Measurement method of average particle size]
Using a particle size analyzer Microtrack MT3300EXII (manufactured by Nikkiso Co., Ltd.), the inorganic particles were ultrasonically applied for 1 minute, and then the particle size was measured. For samples with an average particle ghost of 200 nm or less, take a picture of the inorganic particles with a scanning electron microscope (Hitachi Science Systems Co., Ltd .: SEMEDX3 TypeN) at an arbitrary magnification, and process the taken image using image analysis software. The circle-equivalent diameter of 50 primary particles was measured, and the average particle diameter was calculated by the above formula based on the measured values.

[Measurement method of pore volume and specific surface area]
Using QUADRASORB evo (manufactured by QUAUTACHORME), the specific surface area was measured by the BET multipoint method and the pore volume was measured by the BJH method. Inorganic particles were pretreated (treated at 200 ° C. for 2 hours under vacuum degassing) to remove adsorbed moisture, and then measured.

The test method of each characteristic evaluated in Examples and Comparative Examples is as follows. Each test was carried out under the condition of automatic kneading with a mixing tip attached.

[Measurement of curing time]
The curing time of the kneaded pastes A and B is measured according to ISO4049: 2009. Specifically, a container (4 mmφ × 6 mm: made of Teflon) to which a thermocouple is attached is filled with 0.8 g of the kneaded paste, and the heat generation curve due to the curing reaction is recorded. The time from the start of kneading the paste to the peak of the heat generation curve is defined as the curing time, and the measured values of three times are averaged.

[Curability stability]
The above-mentioned curing time was compared immediately after the preparation of the paste and after storage at 40 ° C. for 5 months, and the rate of change was S for less than ± 20% and A for 20% or more and less than 40% or -20% or more and less than -40%. % Or more and less than 60% or -40% or more and less than -60% was designated as B, and gelled or uncured was designated as C.
Rate of change (%) = [(Curing time after storage at 40 ° C for 5 months / Curing time immediately after preparation) -1] x 100

[Paste stability]
<Color difference>
The paste was discharged from the syringe, and the color tone (CIE L * a * b *) of the paste immediately after preparation and after storage at 40 ° C. for 5 months in the paste containing the transition metal compound was measured, and the color difference ΔE was calculated. ΔE of 0 or more and less than 2 was defined as S, 2 or more and less than 4 was defined as A, 4 or more and less than 8 was defined as B, and 8 or more was defined as C. As for the specific color measurement method, the paste was sampled in a mold with a thickness of 1.0 mm and an inner diameter of 15 mm, both ends were fixed with a thin glass plate with a thickness of 0.15 ± 0.02 mm, and the paste was separated with a thickness of 1.0 mm. Color was measured using a colorimeter (CM-26d: manufactured by Konica Minolta) under the conditions of SCE and a white background.
<Characteristics>
Equivalent amounts of the first and second pastes are discharged from the syringe, the feeling of kneading is confirmed using a spatula, and the pastes that do not change between the pastes immediately after preparation and after storage at 40 ° C for 5 months are A, slightly hardened. Was designated as B, and those in which changes that were clearly difficult to use such as gelation were observed were designated as C.

The above test results were carried out for compositions 1-48, and the results are shown in Table 4. Compositions 1 to 17,21,22,25 to 30, and 32 to 46 that satisfy storage stability and color stability are described as Examples 1 to 40, respectively.

In Examples 1 to 40 in which each component satisfies the constitution shown in the present invention, the dental composition was cured even after storage at 40 ° C. for 5 months, no significant change in color tone was observed, and the dental composition was applied to the oral cavity. It has high storage stability because it can withstand the use as a product. Further, in Examples 7, 11, 14 to 16, 18 to 25, 37, 38, it was confirmed that although the curing time after storage at 40 ° C. for 5 months was shortened or delayed, it was not a significant change in operation. did.

Although the cause of Example 11 is unknown, it is presumed that (d-2) the polymerization promoting effect is lowered by not containing the polymerizable monomer having an acidic group.

In Examples 7, 14, 15 and 16, it is presumed that the transition metal compound adsorbed on the spherical silica or the fluoroaluminosilicate glass lowered the reactivity for some reason.

In Examples 18 and 19, the curing time was shortened after storage at 40 ° C. for 5 months. These are considered to be due to an excessive amount of (b) a thiourea derivative or (c) an organic peroxide having a hydroperoxide group.

In Examples 20 and 38, the curing time was shortened due to the fact that (b) a thiourea derivative and (c) a slightly excessive amount of the transition metal compound with respect to the organic peroxide having a hydroperoxide group were contained. Alternatively, it is considered that a delay has occurred.

In Examples 22, 24, and 26, since the amount of adsorbed transition metal was rather large, it is presumed that the transition metal compound was localized in the composition, resulting in slight discoloration.

In Examples 21, 23, 37, a slight delay was observed in the curing time after storage at 40 ° C. for 5 months. In Example 21, the transition metal compound itself is less than (b) a thiourea derivative and (c) an organic peroxide having a hydroperoxide group, and in Example 23, the amount of the transition metal adsorbed by the transition metal adsorbent is small. It is presumed that this is due to the fact that it is too small.

Example 25 is a composition in which (b) a thiourea derivative and (c) an organic peroxide having a hydroperoxide group of Example 16 are replaced from the respective pastes, and a shortening of the curing time within an allowable range is observed. It is presumed that (c) the activity was unintentionally increased by blending the organic peroxide having a hydroperoxide group and the transition metal compound in the same paste for a long period of time.

In Example 28, (b) the amount of the thiourea derivative was rather small, so it is presumed that some discoloration occurred.

In Example 30, since (b) the thiourea derivative was slightly abundant, it is presumed that some discoloration occurred.

In Example 32, (c) the amount of organic peroxide having a hydroperoxide group was slightly small, so it is presumed that some discoloration occurred.

In Example 36, since (d-2) the amount of the polymerizable monomer having an acidic group was slightly large, it is presumed that some discoloration occurred.

Since Example 40 does not contain any components other than (a) to (d), it is presumed that some discoloration occurs and the paste properties are deteriorated.

The curing time of these dental compositions can be arbitrarily adjusted by adding a plurality of polymerization accelerators and increasing or decreasing the blending amount or the adsorption amount of the transition metal compound. Furthermore, since it is possible to adjust physical characteristics such as bending strength, flexural modulus, and film thickness by appropriately changing the amount of filler to be blended, particle size, etc., dental cements, dental adhesives, etc. It is preferably used as a dental two-paste type polymerizable composition such as a dental room temperature polymerization resin, a dental abutment construction material, and a dental use.

Since Comparative Example 1 did not contain a transition metal compound, it was confirmed that the polymerization promoting effect was not obtained, the curing time immediately after preparation was extremely long, and the curing did not occur after storage at 40 ° C. for 5 months.

In Comparative Examples 2 and 3, although no significant change was observed in the curing time, discoloration of the composition was observed after storage at 40 ° C. for 5 months. It is presumed that the transition metal compound adsorbed in the pores remained for a long period of time, leading to discoloration.

Comparative Example 4 showed discoloration after storage at 40 ° C. for 5 months, and Comparative Example 5 showed gelation after storage at 40 ° C. for 5 months. It is presumed that this was because the transition metal compound was microscopically localized in the paste without being adsorbed by inorganic particles or the like, leading to discoloration or gelation. Further, although the blending amount of the transition metal compound of Comparative Example 4 is almost the same as that of Example 1, it can be considered that the dispersion in the composition is insufficient because the curing time is long.

In Comparative Example 6, although the curing time immediately after preparation was appropriate, it was confirmed that the first paste gelled after storage at 40 ° C. for 5 months. Although the blending amount of the transition metal compound is the same as that in Example 1, the PMMA particles, which are the adsorbed particles, swell or dissolve in the polymerizable monomer to dissolve the dispersed state, and the transition metal compound is localized in the composition. Therefore, it is considered that gelation was induced. In Comparative Example 7 and Comparative Example 8, curing was not achieved.

INDUSTRIAL APPLICABILITY In the field of dentistry, the present invention relates to dental resin cement, dental abutment construction material, dental adhesive, dental coating material, pit fissure filling material, composite resin, dental room temperature polymerization resin, and dental pretreatment. Since it is widely used as a material, a material for a denture base, etc., it can be used industrially.

Claims (7)

(A) A transition metal adsorbent in which a transition metal compound of the 4th period is adsorbed on an inorganic particle that is non-reactive with the transition metal compound of the 4th period.
(B) Thiourea derivative,
It contains (c) an organic peroxide having a hydroperoxide group and (d) a polymerizable monomer.
The (d) polymerizable monomer contains (d-1) a polymerizable monomer having no acidic group.
A dental curable composition characterized by having a pore volume of non-reactive inorganic particles of 0.2 cc / g or less. The dental curable composition according to claim 1, wherein the (d) polymerizable monomer further contains (d-2) a polymerizable monomer having an acidic group. The dental curable composition according to claim 2, wherein (d-2) 1 to 40 parts by weight of the polymerizable monomer having an acidic group is contained with respect to 100 parts by weight of the total amount of the polymerizable monomer. .. A transition metal adsorbent in which the first paste (a) adsorbs a transition metal compound of the 4th period on inorganic particles that are non-reactive with the transition metal compound of the 4th period.
(B) Thiourea derivatives and
(D) Containing a polymerizable monomer
The second paste is (c) an organic peroxide having a hydroperoxide group, and
(D) The dental curable composition according to any one of claims 1 to 3, which comprises a polymerizable monomer. (A) The amount of the transition metal compound adsorbed in the 4th period in the transition metal adsorbent in which the transition metal compound in the 4th period is adsorbed on the non-reactive inorganic particles with the transition metal compound in the 4th period is 0.001 to 0. The dental curable composition according to any one of claims 1 to 4, which is 1 g / m ^2. With respect to 100 parts by weight of the total amount of the polymerizable monomer
(A) 0.05 to 7.5 parts by weight of a transition metal adsorbent in which the transition metal compound of the 4th period is adsorbed on inorganic particles that are non-reactive with the transition metal compound of the 4th period.
(A) 0.001 to 1 part by weight of the transition metal compound contained in the transition metal adsorbent in which the transition metal compound of the 4th period is adsorbed on the inorganic particles that are non-reactive with the transition metal compound of the 4th period.
(B) 0.1 to 4 parts by weight of the thiourea derivative,
(C) The dental curable composition according to any one of claims 1 to 5, which contains 0.1 to 3 parts by weight of an organic peroxide having a hydroperoxide group. With respect to 100 parts by weight of the total amount of the polymerizable monomer
Filler 0.5-350 parts by weight,
Photopolymerization initiator 0.01 to 5 parts by weight,
The dental curable composition according to claim 6, further comprising 0.01 to 5 parts by weight of a polymerization accelerator.